Glycolurile derivatives

ABSTRACT

IN WHICH A is a radical resulting from the removal of at least three atoms of hydrogen replaceable by methylols on atoms of nitrogen of a compound capable of supplying aminoplasts; R1 ie either a hydrogen atom or an alkylor acyl radical comprising less than 4 atoms of carbon; R2 is an aliphatic alkyl or acyl radical comprising at least 10 atoms of carbon or aliphatic alkyl or acyl radical comprising at least 10 atoms of carbon or an alkyl radical comprising at least 2 atoms of carbon and at least one halogen substituent; R3 is a radical resulting from the removal of a hydroxyl from the alcohol group of the addition product of 5 to 30 molecules of identical or different alkylene oxides on an alcohol or an acid; and m, n and p are equal to or greater than 1.   The invention relates to new industrial chemical compounds imparting anti-soiling properties on cellulose and synthetic fabrics said compounds having the general formula:

ilied States Patent [1 1 Savostianofi et al.

[ Dec. 16, 1975 GLYCOLURILE DERIVATIVES [75] Inventors: Dimitri Savostianoff, Asnieres;

Denise Dubos, Paris, both of France [73] Assignee: Nobel Hoechst Chimie, Puteaux,

France 22 Filed: Jan.30, 1973 211 Appl. No.: 328,061

[30] Foreign Application Priority Data 117/l39.5 A; l17/l39.5 R; 260/249.6; 260/249.9; 260/551 C; 260/553 B; 260/615 B Noller, Chemistry of Organic Compounds, 2nd ed., pp. 137-140 8!. 152, Philadelphia, Saunders, 1958. Barker et al. J. Heterocyclic Chem, Vol. 3, p. 354 (1966).

Kamlet, Chem. Abst., Vol. 47, column 3566 (1953). Petersen et al. Chem. Abst., Vol. 76, No. l14770a (1972).

Scheuermann et a1. Chem. Abst., Vol. 55, column 10471 (1961).

Primary ExaminerNatalie Trousoe Attorney, Agent, or FirmKarl W. Flocks [57] ABSTRACT The invention relates to new industrial chemical compounds imparting anti-soiling properties on cellulose and synthetic fabrics said compounds having the general formula:

cn on A CH OR )n cn on in which A is a radical resulting from the removal of at least three atoms of hydrogen replaceable by methylols on atoms of nitrogen of a compound capable of supplying aminoplasts; R ie either a hydrogen atom or an alkylor acyl radical comprising less than 4 atoms of carbon; R is an aliphatic alkyl or acyl radical comprising at least 10 atoms of carbon or aliphatic alkyl or acyl radical comprising at least 10 atoms of carbon or an alkyl radical comprising at least 2 atoms of carbon and at least one halogen substituent; R is a radical resulting from the removal of a hydroxyl from the alcohol group of the addition product of 5 to 30 molecules of identical or different alkylene oxides on an alcohol or an acid; and m, n and p are equal to or greater than 1.

4 Claims, N0 Drawings GLYCOLURILE DERIVATIVES The present invention relates to new compounds for giving cellulose or synthetic fabrics non-stain properties.

The problem of protecting fabrics against staining and soiling has been the subject of numerous works which have led to the perfecting of products, the chemical nature of which is fairly varied and which, for this reason, have fairly different anti-stain properties. There may be cited for example the products which prevent fixing of certain types of stains on the fabrics during wear; this is the case of waterproof, oil-proof and antistatic products, the products which facilitate elimination of soil marks or stains by washing, especially fatty stains (so-called soil release products) and finally the products which prevent redepositing of dirt during washing. While certain products may be particularly active in one of these u'tilizations, they may not be without action in the others.

Amongst the products which facilitate elimination of stains and soiling by washing, the most important are the copolymers containing acrylic acid and the fluorocarbon resins. However, the greater part of the products at present marketed commercially has many disadvantages; they lack permanence, which means that the fariti-staining effect diminishes rapidly during the course of successive washings; few are effective on synthetic fabrics and, generally speaking, almost all make the fabrics disagreeable to the touch.

The products according to the invention permit these disadvantages to be avoided to a great extent: they are permanent, effective on synthetic fabrics and give fabn'cs a soft feel.

The compounds forming the object of the present invention are substances which have the properties of a non-ionic tensio-active agent and furthermore possess suitable reactive groups which enable them to become fixed on textiles. It has been found that such compounds give cellulose fabrics, synthetic fabrics and also mixed fabrics on which they are fixed advantageous non-staining properties.

More' 'particularly, the compounds according to the invention are substances containing several atoms of methylolated nitrogen, partly or wholly etherified or esterified and further comprising in their molecule at least one water-repellent group and at least one hydrophilic group. According to the invention, these compounds thus contain, fixed on the methylol groups:

at least one water-repellent group represented by an aliphatic chain comprising a number of atoms of carbon greater than at least one hydrophilic chain, preferably obtained by polymerization of an alkylene oxide or of a mixture of alkylene oxides;

at least one reactive group enabling the compound to be fixed on textile fibres. I

The compounds in question are represented by the following general formula:

in which:

A represents a radical obtained by removing at least three atoms of hydrogen replaceable by methylols on nitrogens of a poly-nitrogenous compound;

CPI- 0R represents a reactive group acting on textile fibres;

CH OR represents a water-repellent group;

CH OR represents an hydrophilic group;

R is either an atom of hydrogen or a lower acyl or alkyl radical comprising 1 to 4 atoms of carbon; R is an aliphatic acyl oralkyl radical with a long chain comprising at least 10 atoms of carbon or an alkyl radical comprising at least two atoms of carbon and at least one substituting halogen, such as a (CH ),-R in which R, is a perfluorinated alkyl radical and r is a whole number equal to or greater than 1;

R is a radical resulting from the removal of a hydroxyl from the alcohol group of the addition product of 5 to 30 molecules of identical or different alkylene oxides on an alcohol or an acid;

m, n and p may be equal to or greater than 1.

Among the above compounds is a group having the formula crnon or isomeric mixtures thereof, wherein one of R, R R or R is alkyl of l0-l8 carbons, alkanoyl of 10-18 carbons or (CH -R in which r is one and R is a perfluorinated alkyl of 7 carbons; one of R R R or R is (AO),,,R wherein A is ethylene or propylene, m is 5-30 and R is alkyl of l-4 carbons; and the remaining two of R, R R and R are the same and are alkyl of 1-3 carbons. Within this group is a sub-group wherein two of R R R and R are methyl; one of R R R or R is perfluoro-heptyl-methyl; and one of R, R R or R is (CH CH O),,,CH wherein m is 8-10.

The compounds of the invention are prepared by the usual methods from the compounds A (CH OR by reacting the latter, successively with R OH and then R OH in the presence of an acid catalyst, the compounds R OH and R OH being utilized according to a number of mols corresponding respectively to n and p.

The nitrogenous product which forms the radical A is preferably a product capable of supplying amino-plasts, such as for example, glycolurile, melamine, an alkyl or aryl diamino-4,6 s-triazine, dicyan-diamide, biuret and the like.

The radical R is preferably a methyl or acetyl radical, the radical R is an octadecyl radical, stearoyl or perfluoro-heptyl-methyl and the radical R represents the chain of alkylene oxides obtained by the addition of ethylene oxide, propylene oxide or a mixture of the two on methanol or ethanol.

The compounds according to the invention are applied to the fabrics by impregnation in a full bath followed by a fulling in the presence of an acid catalyst or one capable of liberating an acid. They may also be applied at the same time as textile resins of the same type as those used to improve the non-creasing properties of cellulose fabrics or to improve the feel of synthetic fabrics, or any other auxiliary textile resin.

It is, of course, recommended to avoid using them with products known for their aptitude in attracting stains, such as certain silicones or acrylic resins.

After drying in the vicinity of 100C and condensation at about 150C, there are obtained dressings which withstand successive washings and which facilitate the elimination of stains by washing, even in the presence of textile resins. In addition, the fabrics thus treated are soft and agreeable to the touch.

The following non-limitative examples will give a more precise idea of the compounds according to the invention and their application as non-stain anti-soiling agents.

EXAMPLE 1 318 grams (1 mol) of tetra-methoxy-methylglycolurile are heated while stirring with 271 grams (1 mol) of octadecanol-l in the presence of 0.200 grams of paratoluene-sulphonic acid up to 80l00C. The methanol formed during the course of the reaction is collected. When 32 grams (1 mol) of methanol have been collected, there are added 452 grams (about 1 mol) of an alcohol obtained by adding molecules of ethylene oxide to 1 molecule of methanol and 4.5 grams of para-toluene-sulphonic acid. The mixture is heated to 90lO0C until 32 grams (1 mol) of methanol have been distilled. After cooling, there are obtained 950 grams of a waxy mass composed essentially of dimethoxy-methyl, octadecyl-oxy-methyl, methoxydeca (ethylenoxy)-methyl-glycolurile.

EXAMPLE 2 The procedure is the same as that described in Example l, but instead of methoxy-nona (ethylenoxy)- ethanol, there are employed 748 grams (about 1 mol) of methoxypentadeca (ethylenoxy) ethanol obtained by the addition of 16 molecules of ethylene oxide to 1 molecule of methanol. There are thus obtained 1250 grams of a waxy mass composed essentially of dimethoxy-methyl, octa-decyloxy-methyl, methoxy-hexadeca(ethylenoxy)-methyl-glycolurile.

EXAMPLE 3 The operation is the same as in Example 1, but the tetramethoxy-methyl-glycolurile is replaced by 390 grams (1 mol) of hexamethoxy-methyl-melamine. There are thus obtained 1040 grams of tetramethoxymethyl-octadecyloxy-methyl-methoxy-deca(ethylenoxy)-methyl-melamine.

EXAMPLE 4 The procedure is the same as in Example 2, using instead of the tetramethoxy-methyl-glycolurile, 390 grams (1 mol) of hexamethoxy-methyl-melamine. In this way there are obtained 1340 grams of tetramethoxy-methyl-octadecyloxy-methyl-methoxy-hexadeca(ethylenoxy)-methyl-melamine.

EXAMPLE 5 To 318 grams (1 mol) of tetramethoxy-methylglycolurile, there are added 284 grams (1 mol) of stearic acid and the mixture is heated under vacuum at 150-180C until the acid number of the reaction mixture is lower than 5. The mixture is then cooled to 70C and there are added 452 grams (about 1 mol) of methoxy-nona( ethylenoxy)ethanol together with 4 grams of para-toluene-sulphonic acid. The mixture is heated at 80-100C until the elimination of 32 grams (1 mol) of methanol. There are obtained 950 grams of dimethoxy-methyl-stearoyloxy-methyl-methoxy-deca(ethylenoxy) methyl-glycolurile.

EXAMPLE 6 The first part of the operation is carried out as described in Example 5 but in the second part, the methoxy-nona-(ethy1enoxy)-ethanol is replaced by 748 grams (about 1 mol) of methoxy-penta-deca(ethylenoxy)-ethanol, which gives 1250 grams of a product constituted essentially by dimethoxy-methylstearoyloxy-methyl-methoxy-hexadeca(ethylenoxy)- methyl-glycolurile.

EXAMPLE 7 EXAMPLE 8 The operation is the same as for Example 5 for the first part of the reaction but by replacing tetramethoxymethyl-glycolurile by hexamethoxy-methyl-melamine on which stearic acid is reacted. In the second part of the reaction, the methoxy-penta-deca-(ethylenoxy)- ethanol is reacted and there are thus obtained 1350 grams of tetramethoxy-methyl-stearoyloxy-rnethylmethoxy-hexadeca (ethylenoxy)-methy1-melamine.

EXAMPLE 9 A polyester-cotton fabric 67/33 is treated by the product of Example 1 under the following conditions:

The impregnation is effected in a full bath in a solution with a pH value of 4.5-5 containing per liter:

The product of Example 1 50 grams The NKC catalyst of Nobel Hoechst/Chimie (with a base of magnesium chloride) 5 grams The impregnation is followed by a fulling operation with a liquid extraction rate of percent. After drying at C, the product is condensed for 3 /& minutes at C. and then the non-soiling effect is evaluated.

METHOD EMPLOYED FOR THE EVALUATION OF THE NON-SOILING EFFECT The method employed is close to that forming the subject of the AATCC Standard No. 130, 1969. The test is however, more severe, other stains having been added to those provided by this Standard. It consists of carrying out on the fabric to be examined stains having the following compositions:

1. Mixture Active carbon (black Acticarbone 3 S of SOBREP) 2 grams NUJOL" Vaseline oil 20 grams Lanoline 1 gram Trichlor-ethylene 10 grams Arachis oil.

Drained automobile engine oil.

The fabric thussoiledfis kept for 4-hours before washing. The washing is carried out for 12 minutes at 60C, using as a detergent 3 grams per liter of a commercial product SUPER BOZIL of NOBEL BOZEL.

After drying for 45 ininutesin' a drier of the tumbledry type, the washed samples are'compared with the Standard replicas" numbered from -1fto 5 by order of decreasing visibilityof the stain: I

No. l, the stain is very visible; 7

No. 5, the stain has practically disappeared.

In order to define further the results obtained, the FIGS. 1 to 5 have been givensigns of and giving an estimate more or less than the figure indicated.

METHOD USED FORTHE EVALUATION OF THE PERMANENCE OF THE ANTI SOILING EFFECT The permanence of the anti-soiling treatment is assessed by carrying out on other, samples of fabric treated with the anti-soiling dressing, on the one hand a series of 3 washings and, on the other, a series of 10 washings at 60C, following the AATCC Standard 888 of 1969, and then drying for 45 minutes at 70C in the Tumble-Dry. The samples are then conditioned for 24 hours at C i 2 in an atmosphere at 65% i 1 of humidity, after which they are subjected to an estimation of the anti-soiling effect following the method described above.

The results obtained in the assessment of the antisoiling effect and of its permanence after 3 washings and after 10 washings, expressed by FIGS. of 1 to 5, are collected together in the following Table in comparison with an untreated fabric:

Un- Non-soiling treated fabric Stains treated fabric Initial Test after Testafter Test 3 washings l0 washings Mixture l 2 4 4 4- Arachis oil 2 4 4 3* Motor oil I 2 2 l The fabric treated retains practically no trace of the stains of mixture 1 and of the arachis oil, and this nonsoiling effect is wholly preserved after 3 washings; it is still very considerable after 10 washings.

EXAMPLE 10 50 grams Product of Example 1 ARKOFIX NGF of Nobel Hoechst Chimie I50 grams 50 grams Catalyst NKC ofNobel Hoechst Chimie A comparative test is also carried out with the same bath in the absence of the product of Example 1 that is to say solely with the textile resin and the catalyst. There are obtained the results as set out in the Table below:

Y Unlfabric treated with Fabric treated with Stains treated ARKOFIX NGF ARKOFIX Product fabric of Ex. 1

Ini- Test Test lni- Test Test tial after after tial after after test 3 10 test 3 l0 washwashwashwashings ings ings ings Mixture l 2 '2- -2' 2 4+ 3 3 Arachis oil 2 2 2 2 4* v 3 3 Motor oil I l l l 3 2* 2' The non-soiling effect is also very definite.

EXAMPLE 1 l A fabric of percent polyamide is treated with the product of Example I under the same conditions as in Example 9, but with a liquid extraction rate of 55 percent and with a bath having the following composition in grams per liter:

The product of Example 1 65 grams Catalyst NKC of Nobel Hoechst Chimie 6.5 grams The results obtained are as follows:

Non-soiling treated fabric Stains treated fabric Initial Test after Test after Test 3 washings -10 washings Mixture l 3 5 4 4- Arachis oil 2* 4* 4 4 Motor Oil 2 3* 3 3 On pure synthetic textiles, the product is therefore also shown to be very effective.

EXAMPLE 12 A fabric of 100 percent polyamide is treated with the product of Example 1 under the same conditions as in Example 9, but with aliquid extractionrate of 55 percent and with a bath containing, in addition to the product of Example 1, a textile resin with a base of methylolated melamine having a composition in grams per liter:

The product of Example I 65 grams ARKOFIX NM of Nobel HOECHST Chimie 40 grams NKC catalyst of Nobel Hoechst Chimie 18.5 grams A comparative test is carried out with a bath of the same composition but without the product of Example 1.

The following results were obtained:

Fabric treated Fabric treated with 7 The non-soiling product is therefore also effective on synthetic textiles in the presence of a textile resin.

EXAMPLE 13 A polyester/cotton fabric 67/33 is treated by the product of Example 4 under the same conditions as in Example 9, but with a bath having the following composition, expressed in grams per liter:

Product of Example 4 Catalyst NKN of Nobel Hoechst Chimie (comprising zinc nitrate) 50 grams grams The results obtained are as follows:

Treated non-soiling fabric A polyester/cotton fabric 67/33 is treated at the same time with the Example of Examla 4 and with a textile resin comprising dimethylol-dihydroxy-ethyleneurea, utilizing the conditions of application of Example 9, but with a bath having the following composition in grams per liter:

Product of Example 4 50 grams ARKOFIX NGF of Nobel Hoechst Chimie 150 grams Catalyst NKC of Nobel Hoechst Chimie 50 grams A comparative test is carried out with the same bath but without the product of Example 4. These tests gave the following results:

Fabric treated with Fabric treated with ARKOFIX NGF ARKOFIX NGFG Unproduct of Ex. 4 Stains treated lni- Test Test lni- Test Test fabric tial after after tial after after test 3 test 3 l0 washwashwashwashings ings ings ings Mixture l 2 2 2 2 4 3 3 Arachis oil 2 2 '2" 2 4 3 3 Motor oil 1 1' l l 3* 3 2 EXAMPLE Product of Example 4 Zinc chloride 65 grams 3 grams The following results were obtained:

Fabric treated Un- Stains treated Initial Test after Test after fabric Test 3 washings l0 washings Mixture l i 3 5 4 4 Arachis oil 2 4 4 4 Motor oil 2 3 3 3 EXAMPLE 16 A fabric of 100 percent polyamide is treated according to the conditions of Example 9 but with a liquid extraction rate of 55 percent and utilizing a bath containing, in addition to the product of Example 4, a resin comprising methylolated melamine in the following proportions in grams per liter:

Product of Example 4 65 grams ARKOFIX NM of Nobel Hoechst Chimie 40 Grams Zinc chloride 7 Grams A comparative test is also carried 'out with a bath of the same composition but without the product of Example 4. The Table below summarizes the values obtained:

Fabric Treated Fabric Treated with with ARKOFIX NM ARKOFIX NM Unproduct of Ex. 4 Stains treated ini- Test Test ini- Test Test fabric tial after after tial after after test 3 10 test 3 10 Washwashwashwashings ings. ings ings Mixture l 3 2 2 2 5 3 3 Arachis oil 2* 2 3 1 4 4- 3* Motor Oil 2 2 2 l 3 3 2 It is definitely clear from Examples 9 to 16 that the products of the invention have an anti-soiling effect on cellulose fabrics and on synthetic fabrics and that this effect withstands washing. In addition, all the samples of these examples treated with the product according to the invention have a soft feel.

EXAMPLE 17 318 grams (1 mol) of tetramethoxy-methylglycolurile are heated to 95C. while stirring with 496 grams (1 mol) of an alcohol obtained by adding 10 molecules of a mixture of ethylene-oxide-propylene oxide in the proportions of l to l to one molecule of methanol, the whole in the presence of 4 grams of paratoluene sulphonic acid.

The methanol formed during the course of the reaction is collected by distillation under vacuum. When 32 grams or 1 mol of methanol have been collected, there are added 271 grams (1 mol) of octadecanol together with 0.2 gram of paratoluene sulphonic acid. The mixture is heated to l00C until 32 grams (1 mol) of methanol have been distilled. After cooling, there are obtained 1000 grams of a product which is'diluted in water at 33 percent after it has been neutralized with triethanolamine. v

EXAMPLE 18 this effect being the same as in Example 9, another sample of the same fabric was treated under the same conditions with the product of Example 21. The results obtained were as follows:

The procedure is the same as for Example 17, but Nomsomng treated f b i there are employed in the first part 738 grams (1 mol) uhproduct of Product of of alcohol obtained by adding molecules of a mix- Siam treated ExamP1e Example f- T I T T ture of ethylene and propylene oxides 1n the proporis: 6: i: g tions of l to l, on 1 molecule of methanol. 10 test 3 test 3 10 There are thus obtained 1250 grams of product W f f ings ings ings whlch are diluted in water to 33 percent after having Mi tu e l 2 4- 3+ 4+ 2+ 2+ neutralized it with triethanolamine. z on 2 5 3 MOIOX Oil 1 3 2 3 2 1* The procedure is carried out as in Example 17, but the alcohol of the first portion of the reaction is replaced by ll60 grams (1 mol) of an alcohol obtained EXAMPLE 24 by addition of 20 mols of a mixture of ethylene oxide Th previous t t i re eated with the same products and propylene oxide n 1 molecule of butanoli There 20 of Examples 20 and 21, but under the conditions of a e Obtalned 1600 grams of Product which are Example 10, mainly in the presence of a textile resin treated in the same manner as in the previous Example. ARKOFIX NGF. The results obtained were as follows:

EXAMPLE 20 Fabric treated Fabric treated Fabric treated with ARKOFIX NGF with ARKOFlX with ARKOFlX product of product of Example 20 Example 21 Stains Ini- Test Test lni- Test lni- Test Test tial after after tial after tial after after test 3 10 test 3 test 3 l0 wash washwashwashwashings ings ings ings ings Mixture l 2- 2 2 4 2 4 3- 2 Arachis oil 2 2 2 4 2 4 3 3' Motor oil l l l 2 2 2* 2 2 Theisarne procedure is followed as in Example 17, but insteadtof tetramethoxy-methyl-glycolurile, there is EXAMPLE 25 K 99; 90 gra 0f QY- y A 100 percent polyamide fabric is treated under the melamine; After 9 9 there P P F 1050 same conditions as in Example 11 with a bath having grams of a product which is neutralized with triethanolthe f ll i composition i grams per li amine and which is diluted to 33 percent in water.

EXAMPLE 21 Product of Example 20 (expressed in 100%) grams Zinc chloride 3 grams The operation is the same as in Example 18, but utllllzmg grans mol) i i i fi f hg An identical fabric is treated under the same condime amme mstea 0 tetramet oxy'met y yco un 50 tions with the product of Example 21, and the results There are obtained 1300 grams of a product which is diluted to 33 percent in water after it has been neutralized with triethanolamine.

EXAMPLE 22 EXAMPLE 23 A polyester/cotton fabric 67/33 is treated with the product of Example 20 under the same conditions as in Example 9, the concentration of the bath in the product of Example 20 being 50 grams per liter expressed in 100 percent product. The methods used for the assessment of the non-soiling effect and of the permanence of obtained are as follows:

Fabric treated with Product of Fabric treated with Product of The percent polyamide fabric is treated under the conditions of Example 12 with a bath having the following composition in grams per liter:

. The following tests were carried out on the fabric Product of Example 20 (in 100% 50 grams thus treated: A RKOF1X NM grams 1. Estimate of the anti-soiling effect (AATCC test) Zinc Chloride 6 grams 2. Estimate of the anti-soiling effect and of the nonredeposit effect of the soiling substance (CAS- An indentical fabric is treated under the same condi- SELLA test). tions with the product of Example 21.

The results Obtained are as follows. 1. Method Used to Estimate the Anti-Soiling effect Fabric treated Fabric treated Fabric treated with ARKOFIX NM with AKROFIX with ARKOFIX product of product of Example Example 21 Stains lni- Test Test lni- Test lni- Test Test tial after after tial after tial after after test 3 10 test 3 test 3 10 wash washwashwashwashings ings ings ings Mixture 1 2 2 2- 4- 3 4+ 3 3- Arachis oil 2 2 2- 3 3 4- 3- 3- Motor oil 2 2 2 3 3 3 2 2 EXAMPLE 27 2 5 (AATCC Test) 318 grams (1 mol) of tetramethoxy-methyl- This method is that described in Example 9.

glycolurile are heated while stirring with 452 grams (1 mol) of an alcohol derived from the addition of 9.55 molecules of ethylene oxide on 1 molecule of methanol And the Non'Re'Deposlt Effect of the Sollmg and 1.5 grams of paratoluene sulphonic acid. The mix- 30 Substance (CASSELLA Test) ture is heated under vacuum (20 mm.Hg) at 90-100C The method utilized is that described by Dr. R. until there are obtained 32 grams (1 mol) of methanol. KLEBER Soil release, Problematik and Aspekte There are then added 400 grams (1 mol) of perfluoro- Textil Praxis 1969 Heft l, p. 49. It consists of applying heptyl-methanol. Heating is carried out at 120C under mayonnaise with 80 percent of fat content to the mida slight vacuum (0.2 kg/sq cm). After cooling there is 35 die of the fabric to be tested, and then, after drying for 2. Method Used to Estimate the Anti-soiling Effect obtained 1' kg of a product composed essentially of: 2 hours, of dipping the sample into an aqueous disperdimethoxy-methyl-perfluoro-heptyl-methylenoxysion at 1 percent of smoke black; after drying for 2 methy1-methoxy-deca(ethylene-oxy)methylhours in air, the sample is washed by hand for 10 minglycolurile. utes at 60C with a detergent, rinsed and then dried.

The anti-soiling effect is assessed by the elimination by EXAMPLE 28 washing of the stain of mayonnaise and the anti-re- The operation is carried 'out as in Example 27, but deposit effect of the soiling substance by the coloration the tetramethoxy-methyl-glycolurile is replaced by 390 of the fabric outside the stain of mayonnaise.

grams (1 mol) of hexamethoxy-methyl-amine. There For the sake of convenience, the results have been are thus obtained 1.17 kg of tetramethoxy-methyl-perexpressed by numbers of 1 to 6, comparing with stanfluoro-heptyl-methylene-oxy-methyl-methoxydards prepared by the Applicants for that purpose. dewethylee'xy)methylmelamme' ANTT-SOILING EFFECT (Stain of mayonnaise) EXAMPLE 29 No. l The stain is completely black (no anti-soil- A polyester/cotton fabric 67/33 is treated with the ing effect). product of Example 27 in the presence of a so-called No. 2 The stain is represented by a large black reactive textile resin under the following conditions: ring.

The impregnation is carried out in a full bath of a N0. 3 The stain consists of a black ring smaller solution containing, per liter: than for No. 2.

No. 4 The stain consists of a grey ring smaller than Test 1 Test 2 No. 5 The stain is represented by a grey ring which Product of Example 27 10 grams 25 grams ARKOFlX N0 of Nobel Hoechst Chimie can hardly Seen- (Comprising dimethylol- No. 6 There is no trace of the stain of mayonnaise. dihydroxy-ethyIenc-urea) 80 grams 80 grams i N P Hechst Chimie ANTl-REDEPOSIT EFFECT OF SOILING (comprising Zmc mime) grams grams SUBSTANCES (coloration of the fabric outside the stain) The impregnation is followed by a fulling process No. l The fabric is black (no anti-redeposit effect with a liquid extraction rate of percent. After drying 65 of the soiling substances). at C, the product is condensed for 3 minutes at No. 6 The fabric is clean. C and then conditioned for 24 hours at 20C in an The FIGS. 2 to Scorrespond to different grey aspects atmosphere containing 65 percent humidity. of the fabric, the No. 2 being the deepest grey.

In addition to the above methods .1 and 2, the :perma-' nence to washing of the anti-soilingv and anti-redeposit effect is estimated. For this purpose, samples of fabrics treated with the anti-soiling dressing havebeen sub-, jected either to a series of washings or toa series of washings before undergoingthe tests 1 or 2. Each of these washings wasrcarried out in a washing machine same conditions asinExample 29 but replacing the 5 product of Example 27 by the product of Example 28;

the results obtained are collected in the following Tableszfor 10 m 1.2 minutes at 60C, followed by drying for 45 v Y. 't minutes at 70C in a Tumble-Dry machine. L F C TEST) Untreated Anti-soiling treated fabric Stains fabric 7 Initial Test after Test after test A 5 1'5 Y washings washings l0g/l 25g/l IOg/l 25g/l lOgQ 25g/l Mixture l 2 4 4 3 4 3 3 Arachis oil 1 4 5- 4' 4 3 3 Motor oil 1 2 3 2 2 1 2' The results obtained in the various tests in the treated fabric are collected in the Tables given below in comparison with a fabric which is untreated or treated only ANTI-SOILING EFFECT AND ANTI-REDEPOSIT EFFECT OF SOILING SUBSTANCES (CASSELLA Test) Anti-soiling treated fabric Untreated Effect fabric Initial Test after Test after test 5 l5 washings washings IOg/l g/l IOg/l 25g/l lOg/l 25g/l Anti-soiling 2 4 4 4' 4- 3 4- Anti-redeposit of soiling 2 4 4 3 3 2 3' substances with reactive reSin- I The product of Example 28 also has valuable anti- L ANTLSOLING EFFECT (AATCC TEST) soiling and anti-redeposit properties.

Anti-soiling treated fabric 2. ANTI-SOILING EFFECT AND ANTI-REDEPOSIT EFFECT OF SOILING SUBSTANCE (CASSELLA It will of course be understood that the present invention has been described solely by way of explanation and not in any limitative sense and that any useful Test) modification may be made thereto without thereby Anti-soiling treated fabric Stains Untreated fabric Initial Test after Test after test 5 l5 washings washings lQg/l 25g/l lOg/l 25g]! l0g /l ZSgll Anti-soiling 2 5 5 5 5 4 3 Anti-redeposit of soiling 2 5 5 3 4 3 4 substances The product of Example 1 thus had advantageous anti-soiling and anti-redeposit properties; in addition, the feel of the samples is soft and agreable.

departing from its scope as defined in the appended claims.

We claim: 1

l, A compound of the formula or isomeric mixtures thereof, wherein one of R, R, R, or R is alkyl of lO-l 8 carbons, alkanoyl of -18 carbons or (Cl-l ),-R in which 1' is one and R is a perfluorinated alkyl of 7 carbons; one of R, R R or R is (AO),,,R wherein A is ethylene or propylene, m is 5-30 and R is alkyl of l-4 carbons; and the remaining two of R, R R and R are the same and are alkyl of l-3 carbons.

2. A product in accordance with claim 1 which is a waxy mass composed essentially of dimethoxy-methyl, octadecyl-oxy-methyl, methoxy-deca (ethylenoxy)- methyl-glycolurile.

3. A compound in accordance with claim 1 wherein two of R, R, R, and R are methyl; one of R, R R or R" is octadecyl or stearoyl; and one of R, R R or R is (CH CH O),,,CH wherein m is 10 or 16.

4. A compound in accordance with claim 1 wherein two of R, R R, and R are methyl; one of R, R R or R is perfluoro-heptyl-methyl; and one of R, R, R, or R is (Cl-l Cl-l O),,,CH wherein m is 8-10. 

1. A COMPOUND OF THE FORMULA
 2. A product in accordance with claim 1 which is a waxy mass composed essentially of dimethoxy-methyl, octadecyl-oxy-methyl, methoxy-deca (ethylenoxy)-methyl-glycolurile.
 3. A compound in accordance with claim 1 wherein two of R1, R2, R3, and R4 are methyl; one of R1, R2, R3, or R4 is octadecyl or stearoyl; and one of R1, R2, R3, or R4 is (CH2CH2O)mCH3 wherein m is 10 or
 16. 4. A compound in accordance with claim 1 wherein two of R1, R2, R3, and R4 are methyl; one of R1, R2, R3, or R4 is perfluoro-heptyl-methyl; and one of R1, R2, R3, or R4 is (CH2CH2O)mCH3 wherein m is 8-
 10. 